JPS5928521B2 - Nematicidal composition - Google Patents

Description

[Detailed Description of the Invention] In recent years, plant-parasitic soil nematodes have attracted attention as a major factor that inhibits production of agricultural crops, and damage tends to increase year by year, especially due to the increasing variety of vegetables and continuous cropping due to the diversification of garden crops. Therefore, there is a strong desire for preventive measures against the disease.
The development of safe and effective drugs is desired.

As a result of extensive research on compounds having an acetylene group, the present inventors found that the general formula REC-C-R2 (
In the formula, R1 is nitro or halogen.

Phenyl group optionally substituted with methoxy, lower alkyl or cyan, pyridyl group optionally substituted with methyl, chenyl group optionally substituted with C2H500C-, cyclopentenyl optionally substituted with methyl group, cyclohexenyl group optionally substituted with methyl, furyl group optionally substituted with methyl, styryl group, ru, formyl, methoxy, carboxy, -0H1
phenyl group substituted with nitro, amino, carbonylamide, oxymethyl, halogen or cyan; cyclohexenyl group optionally substituted with methoxy; pyridyl group optionally substituted with methyl; Represented by optionally substituted furyl group, chenyl group, quinolyl group, thiazolyl group, cyclopentenyl group, -CH-(OC2H6)2 group, vinyl group, propenyl group, inzorobenyl group, styryl group, ethynyl group. The present invention was completed by discovering that the immersion method of a group of compounds used in the nematicidal test was highly effective in nematicidal tests.

Next, acetylene derivatives are illustrated in Table 1.
The compounds illustrated in the table do not limit the types of acetylenes according to the present invention.

The compounds according to the present invention are generally known compounds that can be produced as follows.

For example, there is a method in which copper acetylide prepared in advance is condensed with a halogenoalkene in pyridine or DMF at 40 to 100°C.

(J, Burdon, etal, Chem, C
ommun, 1967.1259).

Alternatively, when a catalytic amount of copper(I) iodide and a palladium complex are added to a diethylamine solution of monosubstituted acetylene and halogenoalkene, coupling occurs smoothly at room temperature.

(L, Ca5sar, J, Organomet, C
hemo, 93.253 (1975)) The present inventors mainly synthesized by this method.

Diacetylene compounds are prepared using Eglton coupling method CG, E.
glinton.

WlMe Crae, Adv, Org, C
hem, 4.225(1,963), l.

That is, it can be easily obtained by heating a pyridine solution of monosubstituted acetylene to which excess acetic acid has been added to 60 to 70°C.

Production Example 1 Production of Compound No. 3 Phenylacetylene IO,7P (0.105 mole) dissolved in 580 ml of ethanol was poured into an ammoniacal aqueous solution of 20.01 (0.105 mole) of copper iodide.

After stirring for 15 minutes, the precipitate was separated, washed with water, ethanol and ether, and washed with phenylacetylene steel 13.4
I got f.

7,1 dissolved in 100 TLl of pyridine under nitrogen flow
? (0.03 mole) of p-iodoanisole, the above phenylacetylene steel 5, OS' (0.03 m
ole) and stirred at 120°C for 10 hours.

After cooling, the mixture was diluted with water, extracted with ether, and the organic layer was washed successively with hydrochloric acid, a 5% aqueous sodium bicarbonate solution, and water, and dried over anhydrous sodium sulfate.

The crude product obtained by removing the solvent under reduced pressure was decolorized with activated carbon and recrystallized from hot methanol to obtain 6,2 compound 3 (yield 98.5%).

mp58-59°C Production Example 2 Production of Compound No. 23 Under nitrogen flow, 100rr of bis(triphenylphosphine)palladium chloride 470mm (1mmole) and p-iodotoluene 21.82(0.1mole)
Copper(I) iodide 95 in a mixture of Ll diethylamine solution
After adding (0.5 mmole), acetylene gas was introduced for 6 hours at room temperature.

Diethylamine was removed under reduced pressure, water was added, and the mixture was extracted with benzene.

After concentrating the organic layer, it was passed through an alumina column to remove the catalyst and the solvent was removed to obtain a crude product.

This was recrystallized from ethanol to obtain 19.5P compound 2.
3 was obtained (yield 85%).

mp136°C Production Example 3 Production of Compound No. 30 Under nitrogen flow, bis(triphenylphosphine)palladium acetate 414m9 (0.8mmole), 2
-bromothiophene 52.6? (0,2rnole
), phenylacetylene 20.4 ? (0,2mo
A mixture of 100'rrLl and piperidine was stirred at 100°C for 0.5 hour.

After cooling, it was diluted with ether and the residue was separated.

The crude product was concentrated under reduced pressure and the crude product was recrystallized from ethane to obtain 191 compound 30 (yield 53%).

mp50-50.5℃ Production Example 4 Preparation of Compound No. 32 Under nitrogen flow, bis(triphenylphosphine)palladium chloride 235m9 (0.5 mmole) and iodized needles i) i 907n9 (1 mmole), 2-
Bromopyridine 31.6 y (0,2 mole) and phenylacetylene 20.4 ? (0.2 mole
) diethylamine solution was stirred at room temperature for 3 hours.

Diethylamine was removed under reduced pressure, water was added, and the mixture was extracted with benzene. After concentrating the organic layer, it was passed through an alumina column to remove the catalyst, and the solution was removed to obtain a crude product.

Recrystallize this from ethanol to 32.2? Compound 3 of
2 was obtained (yield 90%).

mp34°C Production Example 5 Production of Compound No. 51 Bis(triphenylphosphine)palladium acetate 207mI under nitrogen flow (0.4mmole),
■-Bup Moprohen 12.1? (0.1 mole
), phenylacetylene 10.2P (0.1 mole
) and triethylamine 80 r/Ll.
Stirred at 0°C for 1 hour.

After cooling, dilute with ether, separate the residue, and concentrate the oral fluid under reduced pressure.

The obtained crude product was concentrated under reduced pressure to obtain 12.5f of the target product (yield: 88%).

bp6 Low 67℃/1 mm Production Example 6 Method for producing compound No. 52 Bis(triphenylphosphine)palladium chloride 23.5 mmole (0.05 mmole) under nitrogen stream
and 1-bromocyclopentene 4.41P (30 mmol
e) and phenylacetylene 3.06S' (30m
A solution of 760 rnl of diethylamide was stirred at room temperature for 3 hours.

Diethylamine was removed under reduced pressure, water was added and extracted with benzene, and the organic layer was passed through an alumina column and concentrated to obtain a crude product.

This was distilled under reduced pressure to obtain the desired product 4.5.1' (yield 90%).

bp90℃/1 mrrtManufacturing exampleManufacturing method of compound No. 55Copper acetate (6) - hydrate salt 14.7 f? (0,074m
ole), methanol 150ml, pyridine 149r
Add 3.7P of phenylacetylene to a homogeneous solution of Ill at room temperature.
A solution of (0,036 mole) in 50 rnl of methanol was added dropwise.

After stirring at 60-70°C for 3 hours, the mixture was poured into 18N sulfuric acid.

After extraction with ether, drying the organic layer and removing the solvent,
The residue was adsorbed on alumina and diluted with hexane-ethyl acetate (9
:1) was eluted.

After distilling off the solvent, recrystallization from ethanol yielded 3 grams of compound 5.
5 was obtained (yield 80%).

mp88-90℃ Production Example 8 Production of Compound No. 67 Under nitrogen flow, bis(triphenylphosphine)palladium chloride 470Tru? (1mmole) and
■-Bromocyclohexene16. IP (0.1 mol
After adding 95 Da (0.5 mmole) of iodide to the mixture of 100 ml diethylamine solution in e), acetylene gas was introduced at room temperature for 6 hours.

Diethylamine was removed under reduced pressure, water was added, and the mixture was extracted with benzene.

The organic layer was passed through an alumina column, concentrated under reduced pressure, and then distilled under reduced pressure to obtain the target product of 12.5P (yield 70%) bp
126-128°C/3-strike Production Example 9 Preparation of Compound No. 71 Under a nitrogen stream, 470 m9 (1 mmole) of bis(triphenylphosphine)palladium chloride and methyl trans-3-bromoacrylate16. Fl (0,1m
ole ) of 100ml diethylamine and 10rILl
■)95～(
0.5 mmole), then add 5 mmoles of acetylene gas.
Introduced for hours at room temperature.

The amine was removed under reduced pressure, water was added, and the mixture was extracted with benzene.

The organic layer was passed through an alumina column, concentrated under reduced pressure, and then recrystallized from ethanol to obtain 10 g of compound 71 (yield: 60
%).

mp 120°C The active ingredient compounds of the composition of the present invention may include pentachloronitrobenzene (PCNB), bis(
dimethylthiocarbamoyl) disulfide, tetrachloroisophthalonitrile, 3-hydroxy-5-methylisoxazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, N-(trichloromethylthio)-4- Bactericidal agents such as cyclohexene-2-dicarboximide, N-(1,1,2,2-tetrachloroethylthio)-4-cyclohexene-1,2-dicarboximide, chloropicrin, and 1,2-dibromoethane , ■・Nematicides such as 3-dichloropropane and 12-dichloropropane, bis(2-chloro-1-methylethyl)-ether, furomomethane, sodium (ammonium) N-methyldithiocarbamate, and organophosphorus-based It can also be used in combination with insecticides, carbamate insecticides, chlorine insecticides, various herbicides, and fertilizers, or as a mixture.

Next, the effects of the nematocidal composition of the present invention will be shown by test examples.

Test Example 1 The test nematode was a 1-inch nematode cultivated indoors from alfalfa callus.
usCoffee).

Each drug was dissolved in methanol to a concentration of 1%, and this was diluted with a 0.1% aqueous EPAN420 solution to a predetermined concentration.

Dispense 101 nl of each diluted solution into a Siracian watch glass,
150-200 nematodes per clock, under darkness, 25
Growth was controlled at ℃ for 48 hours.

Thereafter, the nematocidal rate was determined by examining whether the animals were alive or dead under a binocular microscope.

The test was repeated four times. The results are shown in Table 2.

Test Example 2 In the same way as Test Example 1, Pratylenc nematode was cultured indoors using alfalfa callus.
hus Coffeeae) was used.

Each test drug was prepared into a 20% emulsion and used.

The contents of the formulation were as follows: 20 parts by weight of each compound used in the present invention, 70 parts by weight of xylene and 10 parts by weight of polyoxyethylene nonylphenyl ether were mixed to form an emulsion.

This formulation was diluted with water to the desired concentration. 1 of each dilution
0r/11 portions were dispensed into Syracius watch glasses, 150 to 200 nematodes were placed in each watch glass, and growth was controlled at 25°C in the dark for 48 hours.

Thereafter, the nematocidal rate was determined by examining whether the animals were alive or dead under a binocular microscope.

The test was repeated five times. The results are shown in Table 3.

Claims (1)

Scope of Claims: (In the formula, R1 is a phenyl group optionally substituted with nitro, nohogen, methoxy, lower alkyl or cyan, a pyridyl group optionally substituted with methyl, C2H500
Chenyl group optionally substituted with C-, cyclohentenyl group optionally substituted with methyl, cyclohexenyl group optionally substituted with methyl, zolyl group optionally substituted with methyl, styryl group, formyl, methoxy, carboxy, -oH1 nitro, amino, carbonylamide, oxymethyl, phenyl group optionally substituted with halogen or cyan, cyclohexenyl group optionally substituted with methoxy, optionally substituted with methyl pyridyl group, furyl group optionally substituted with halogen, nitro or methyl group, chenyl group, quinolyl group, thiazolyl group, cyclopentenyl A4,
CH(OC2H5) 2 group, vinyl group, propenyl group, impropenyl group, styryl group, ethynyl-CH=
It is characterized by containing as an active ingredient at least one or two or more compounds selected from the following: CH-COOCH3 group, -CH=CH-COCH3 group, -CyoC-CH=CH-COOCH3 group. A nematocidal composition.